title: Indium(III)-catalyzed reductive bromination and iodination of carboxylic acids to alkyl bromides and iodides: scope, mechanism, and one-pot transformation to alkyl halides and amine derivatives.
abstract: Highly effective indium(III)-catalyzed reductive bromination or iodination of a variety of carboxylic acids with 1,1,3,3-tetramethyldisiloxane (TMDS) and a source of bromine or iodine is described. This functional group interconversion has high tolerance for several functional groups, such as halogens, a hydroxy group, a nitro group, an olefin part, and a sulfide moiety. This indium catalytic system is also applicable to the reductive iodination of aldehyded, acyl chlorides, and esters. Furthermore, this reducing system can be applied to the one-pot synthesis of alkyl halides and amine derivatives via the addition of nucleophiles. Insight into the reaction mechanism was gained via the time course of (1)H and (13)C NMR monitoring experiments and the corresponding stepwise reactions.
authors.affiliation: Department of Pure and Applied Chemistry, Faculty of Science and Technology, Tokyo University of Science (RIKADAI) , Noda, Chiba 278-8510, Japan.
authors.forename: Toshimitsu
authors.initials: T
authors.lastname: Moriya
authors.forename: Shinichiro
authors.initials: S
authors.lastname: Yoneda
authors.forename: Keita
authors.initials: K
authors.lastname: Kawana
authors.forename: Reiko
authors.initials: R
authors.lastname: Ikeda
authors.forename: Takeo
authors.initials: T
authors.lastname: Konakahara
authors.forename: Norio
authors.initials: N
authors.lastname: Sakai